Use of silicon-containing precursor compounds of an organic acid as a catalyst for cross-linking filled and unfilled polymer compounds

Abstract

The invention relates to the use of a silicon-containing precursor compound of an organic acid, particularly an olefinic silicon-containing precursor compound of an organic acid and/or of a tetracarboxyl silane, for the production of unfilled and/or filled polymer compounds, polymers, or filled plastics, such as granules or finished products, made from thermoplastic base polymers and/or monomers and/or prepolymers of the thermoplastic base polymers. A finished product is an item, such as a molded body, particularly a cable, hose, or pipe. The invention further relates to a master batch comprising the silicon-containing precursor compound.

1 . A method for catalyzing a silane hydrolysis and/or silanol condensation, comprising:
 contacting a silane and/or silanol with at least one silicon comprising precursor compound of an organic acid as a silane hydrolysis catalyst and/or a silanol condensation catalyst.   
     
     
         2 . The method according to  claim 1 , wherein
 the at least one silicon comprising precursor compound of an organic acid corresponds to general formula I and/or II
   (A) z SiR 2   x (OR 1 ) 4-z-x    (I)
 
   (R 1 O) 3-y-u (R 2 ) u (A) y Si-A-Si(A) y (R 2 ) u (OR 1 ) 3-y-u    (II)
 
   wherein   mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that in the formula I z+x is smaller than or equal to (≦) 3, and in the formula II y+u is independently smaller than or equal to (≦) 2,   A is mutually independently in the formula I and/or II a monovalent olefin group, and A in the form of a divalent moiety in the formula II is a divalent olefin group,   R 1  corresponds, mutually independently, to a carbonyl-R 3  group, wherein R 3  corresponds to a substituted or unsubstituted hydrocarbon moiety, and   R 2  corresponds, mutually independently, to a substituted or unsubstituted hydrocarbon group.   
     
     
         3 . The method according to  claim 1 , wherein
 the at least one silicon comprising precursor compound of an organic acid is applied to a carrier material, or encapsulated and/or embedded into the carrier material.   
     
     
         4 . The method according to  claim 1 , the contacting is in a monosil process, in a sioplas process, and/or in a copolymerization. 
     
     
         5 . The method according to  claim 1 ,
 wherein   the silicon comprising precursor compound of an organic acid is employed in a monosil process, or a sioplas process with at least one thermoplastic parent polymer or in a copolymerization process with at least one monomer and/or prepolymer of the at least one thermoplastic parent polymer, in the presence of at least one free-radical generator.   
     
     
         6 . The method according to  claim 1 , wherein at least one unfilled Si-crosslinked compounded polymer material and/or at least one filled Si-crosslinked compounded polymer material, and/or corresponding filled Si-crosslinked polymer or unfilled Si-crosslinked polymer comprising at least one thermoplastic parent polymer is produced. 
     
     
         7 . The method according to  claim 1 ,
 carried out in the presence of a thermoplastic parent polymer, a silane-grafted parent polymer, or a silane-copolymerized parent polymer, and/or in the presence of a monomer and/or prepolymer of said parent polymers.   
     
     
         8 . The method according to  claim 1 , carried out together with an organofunctional silane compound. 
     
     
         9 . The method according to  claim 8 , wherein
 the organofunctional silane compound corresponds to an unsaturated alkoxysilane, represented by general formula III
   (B) b SiR 4   a (OR 5 ) 3-b-a    (III)
 
   wherein   mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that in the formula III b+a is smaller than or equal to (≦) 3,   B, mutually independently, is a monovalent (R 7 ) 2 C═C(R 7 )-E q - group in the formula III, wherein R 7  are identical or different, and R 7  is a hydrogen atom or a methyl group or a phenyl group, the group E is a group selected from the group consisting of —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, and —C(O)O—(CH 2 ) 3 —, q is 0 or 1, or isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or corresponds to an R 6 -D p -[C(R 6 )═C(R 6 )—C(R 6 )═C(R 6 )] t -D p - group, wherein R 6  are identical or different, and R 6  is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group, or a methyl group or a phenyl group, groups D are identical or different, and D is a group selected from the group consisting of —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, and —C(O)O—(CH 2 ) 3 —, and p is 0 or 1, and t is 1 or 2,   R 5  is, mutually independently, methyl, ethyl, n-propyl, and/or isopropyl, and   R 4  is, mutually independently, a substituted or unsubstituted hydrocarbon group.   
     
     
         10 . The method according to  claim 1 , carried out together with at least one other silanol condensation catalyst selected from the group consisting of dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin di(2-ethylhexanoate), dioctyltin di(isooctylmercaptoacetate), dibutyltin dicarboxylate, monobutyltin tris(2-ethylhexanoate), dibutyltin dineodecanoate, laurylstannoxane, dibutyltin diketonoate, dioctyltin oxide, dibutyltin diacetate, dibutyltin maleate, dibutyltin dichloride, dibutyltin sulfide, dibutyltin oxide, an organotin oxide, monobutyltin dihydroxychloride, a monobutyltin oxide, and dibutyltin bis(isooctylmaleate). 
     
     
         11 . A product, a molding, a cable, or a pipe, produced by the method according to  claim 1 . 
     
     
         12 . A masterbatch, comprising:
 at least one silicon comprising precursor compound of an organic acid and one free-radical generator.   
     
     
         13 . A masterbatch comprising wherein
 (i) at least one silicon comprising precursor compound of an organic acid of formula I and/or II,
   (A) z SiR 2   x (OR 1 ) 4-z-x    (I)
 
   (R 1 O) 3-y-u (R 2 ) u (A) y Si-A-Si(A) y (R 2 ) u (OR 1 ) 3-y-u    (II)
 
   wherein   mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that in the formula I z+x is smaller than or equal to (≦) 3, and in the formula II y+u is independently smaller than or equal to (≦) 2,   A is mutually independently in the formula I and/or II a monovalent olefin group, and A in the form of a divalent moiety in the formula II is a divalent olefin group,   R 1  corresponds, mutually independently, to a carbonyl-R 3  group, wherein R 3  corresponds to a substituted or unsubstituted hydrocarbon moiety, and   R 2  corresponds, mutually independently, to a substituted or unsubstituted hydrocarbon group,   (ii) optionally one free-radical generator, and   (iii) optionally one organofunctional silane compound, or one unsaturated alkoxysilane, of formula III,
   (B) b SiR 4   a (OR 5 ) 3-b-a    (III)
 
   wherein   mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that in the formula III b+a is smaller than or equal to (≦) 3,   B, mutually independently, is a monovalent (R 7 ) 2 C═C(R 7 )-E q - group in the formula III, wherein R 7  are identical or different, and R 7  is a hydrogen atom or a methyl group or a phenyl group, the group E is a group selected from the group consisting of —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, and —C(O)O—(CH 2 ) 3 —, q is 0 or 1, or isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or corresponds to an R 6 -D p [C(R 6 )═C(R 6 )—C R 6 )═C(R 6 )] t -D p - group, wherein R 6  are identical or different, and R 6  is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group, or a methyl group or a phenyl group, groups D are identical or different, and D is a group selected from the group consisting of —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, and —C(O)O—(CH 2 ) 3 —, and p is 0 or 1, and t is 1 or 2,   R 5  is, mutually independently, methyl, ethyl, n-propyl, and/or isopropyl,   R 4  is, mutually independently, a substituted or unsubstituted hydrocarbon group,   and at least one of the above components A, B, and/or C is on a carrier or has been encapsulated.   
     
     
         14 . The masterbatch as claimed in  claim 12 , further comprising
 a thermoplastic parent polymer, a silane-grafted parent polymer, a silane-copolymerized parent polymer, and/or monomer, and/or prepolymer, of said parent polymers, and/or a mixture of these.   
     
     
         15 . The method according to  claim 2 , wherein the precursor compound of an organic acid is of the formula I and/or II, and
 wherein the contacting is in a monosil process, in a sioplas process, or in a copolymerization process.   
     
     
         16 . The method according to  claim 2 , wherein the precursor compound of an organic acid is of the formula I and/or II
 a silicon-containing polymer, or compounded polymer material, or of an unfilled crosslinked polymer, and/or of a filled crosslinked polymer is produced.   
     
     
         17 . A product comprising the silicon precursor compound of an organic acid and/or a product of the hydrolysis and/or condensation thereof, according to  claim 1 . 
     
     
         18 . The method according to  claim 2 , wherein R 1  corresponds, mutually independently, to the carbonyl-R 3  group, wherein R 3  corresponds to the substituted or unsubstituted hydrocarbon moiety having from 1 to 45 carbon atoms.